chem 125 lecture 68 4/15/08 projected material this material is for the exclusive use of chem 125...
DESCRIPTION
11 33 conrotationdisrotation Möbius 22 Hückel connectivity requires twist in 1 of 2 ways Hückel Transition State Motion 11 22 33 44 22 11 33 44 55 66 22 11 33 44 55 66 11 22 33 44 top touches top (even # of nodes) top touches bottom (odd # of nodes) ! 22 11 33 44 55 66TRANSCRIPT
Chem 125 Lecture 684/15/08
Projected material
This material is for the exclusive use of Chem 125 students at Yale and may not
be copied or distributed further.
It is not readily understood without reference to notes from the lecture.
Pericyclic Reactions(in which transition states are “aromatic”)
Cycloadditions: Diels-Alder
Electrocyclic Reactions
13
conrotation disrotationMöbius
2
Hückelconnectivity
requires twistin 1 of 2 ways
Hückel
Transition StateMotion
1
2
3
4
21
3
4
5
6
21
3
4
5
6
1
2
3
4
top touches
top(even #
of nodes)
top touches
bottom(odd # of nodes)
! 21
3
4
5
6
Sec. 27.2pp. 1343-1346
(shown backwards in our text;same favored “aromatic”
conrotatory transition state)
CON4e
CON for 4nCON8e
DIS6e
DIS for 4n+2
2
Transition State HOMO-1
1
disrotation6e Hückel
bottom touches top(odd # of nodes)
top touches top(even # of nodes)
conrotation4e Möbius
Molecules of C4H4 will react with one another unless isolated.
Is cyclobutadiene antiaromatic (4n)?Make it and see.
OO O
OMöbius conrotation
impossible because of product strain
OO
+ O=C=O
h
h
Photochemistry changes electrocyclic preference to disrotation, because an electron is promoted to the next MO
with opposite symmetry.
Photochemistry changes preference of (reverse) cycloaddition too, allowing cyclobutane to become two double bonds.
Make one moleculeper cage
. . ... .. .
..... .
...
.
...
as guestBenzene
Antiaromaticupfield shift?
Most shift comes fromother rings, still ~1.5ppm above benzene
Normal
Making & Studying“antiaromatic”Cyclobutadiene
above center of 8 benzene rings
Opening Dewar Benzene
(1866)
Calculated Isomers of Benzene
(2004)
84 calculated to be < 100 kcal above benzene.
6 > 100 kcal above benzene have been prepared.
Dewar Benzene (1963) is 74 kcal above benzene but lasts 2 days at room temperature!
t1/2 = 2 days (room temp)
-11 kcal
-75 kcal
25
33
conrotatory
disrotatory
more strain
aromatic
66 kcal/mole more exothermic,but only 8 kcal/mole “faster”
But shouldn’t “aromatic” 6--e transition state be good for disrotation?
It is more fundamental that LUMO doesn’t overlap HOMOs (& vice versa).
Making & Studying“antiaromatic”Cyclobutadiene
To discuss making this “clamshell” we’ll
need to learn some more reactions:
Electrophilic Aromatic Substution
and
Carbonyl Reactions
Electrophilic Aromatic
Substitution
Electrophilic Aromatic Substitution
H
HH
H
H
H
D2SO4
H
HH
H
D
H
Sec. 16.4
H
HH
H
H
H
D
via A/D intermediate
+
D2SO4C6D6
etc.
Observable!
Or other electrophiles in place of D+
e.g. NO2+, Br+, HOSO2, R+, R-C=O R-C=O+HOSO2
+
H3C CH3
H3C
H3C
CH3
CH3
CH3
+
A
C C
B
D
B
1H vs. 1Hcorrelation in time
H3C CH3
H3C
H3C
CH3
CH3
CH3
+
CH3
CH3H3C
H3C
CH3
CH3
CH3
+
A
A
C C
B
D
B
C
C
B
D
B
0.3 sec 40°C
CA
DB
Remember
+
+
+
SHMo2 (Simple Hückel Molecular Orbital Program)
Benzene Pentadienyl
Cation addition converts ring to chain.
H
HH
H
H
H
D+
H
HH
H
H
H
D
+
Locus ofodd electron in radical,
+ charge(LUMO)
in cation.
- charge (HOMO)
in anion,SOMO
(nonbonding)
++
+
Cf.
X
NO2
++
+ +
HO2N
X
+ ++
+
H
O2N
X
+
+ +
H
Substituent Effects on RateX
O2N
X
O2N
X X
NO2
+ +NO2
+
(from HONO2/H2SO4)
X Relative Rate (overall)
H [1] Cl 0.03 NO2 6 10-
8
CH3 25 OH 1000
(CH3)3N+ 1 10-
8
donation / withdrawal
(or ) e-donation eases formation of cation intermediates
(or ) e-withdrawal retards formation of cation intermediates
End of Lecture 68April 15, 2009